EP1086162B2 - Corps moules et couches nanostructures et leur production a l'aide de precurseurs stables solubles dans l'eau - Google Patents
Corps moules et couches nanostructures et leur production a l'aide de precurseurs stables solubles dans l'eau Download PDFInfo
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- EP1086162B2 EP1086162B2 EP99920614.7A EP99920614A EP1086162B2 EP 1086162 B2 EP1086162 B2 EP 1086162B2 EP 99920614 A EP99920614 A EP 99920614A EP 1086162 B2 EP1086162 B2 EP 1086162B2
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- process according
- alcohol
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- nanostructured
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
- C03C1/008—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route for the production of films or coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2214/00—Nature of the non-vitreous component
- C03C2214/12—Polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
- Y10T428/2995—Silane, siloxane or silicone coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Definitions
- the present invention relates to nanostructured molded articles and layers and their preparation via stable water-soluble precursors and in particular nanostructured molded articles and layers which are suitable for optical purposes.
- JP-A-53-6339 the synthesis of a composite in which, starting from a reactive organically modified silane and an inert organically modified silane, the hydrolysis in the presence of aqueous silica sol and phosphoric acid is carried out as a catalyst for the hydrolysis. In this case, the alcohol formed in the condensation reaction is not removed.
- JP-A-63-37168 describes the synthesis of a composite of dispersed in an aqueous medium and free-radically crosslinking monomers based on acrylate and organically modified silanes, wherein the organic radical of these silanes also represents a radically crosslinking system, in the presence of colloidal silica and nonionic surfactants. Hydrolysis and condensation reactions are carried out in a separate process step. Again, the alcohol formed in the condensation reaction is not removed.
- JP-A-63-37167 for a system in which the silane component has cationic crosslinking groups.
- US-A-5411787 describes the synthesis of a composite of water-dispersed polymeric binders, at least one aminosilane component and colloidal particles having a particle size of less than 20 nm. Also in this case, the alcohol formed by the hydrolysis of the silane is not removed.
- WO 99/51793 a document to be considered in accordance with Article 54 (3) and (4) EPC 1973 for the Contracting States BE, CH, ES, FR, GB, IT, LI, NL, PT, SE, relates to a metallic subglacial sealant, consists of at least one silane derivative and colloidal silica and / or colloidal silicate.
- the object of the present invention was thus to provide a process for the preparation of nanostructured moldings and layers, preferably those which are suitable for optical purposes, via stable water-soluble intermediates.
- aqueous, electrostatically stabilized (and thus extremely concentration-sensitive) colloidal suspensions can be coated with reactive monomeric or oligomeric components (silanes or precondensates thereof) and thereby concentrate the star-like effect ( Z. Electrochem., 508 (1924 )) of the aggregation of two particles in the same direction during their approach, but in particular also the otherwise spontaneous chemical reactions between reactive surface groups of two particles, not show.
- the concentration and shift of the reaction equilibrium on the product side to form the surface condensates is achieved by the removal of the resulting in the condensation reaction of the alcohol (usually methanol or ethanol), with very high storage stability of the condensates (> 14 days) relative low residual solvent contents (usually not more than 20 wt .-% and in particular not more than 10 wt .-%).
- surface modifier particles eg hydrogen bonding or metal-oxygen bonding (-Al-O-Si-, -Ti-O-Si-etc., See eg Chem. Mat. 7 (1995), 1050-52 ) can be reversed when supplied with heat, the process described above, so that crosslinking of the particles can be carried out under solidification.
- a further reaction can also take place via appropriately selected organic groups on the surface modifier (eg reaction of these groups with one another).
- aqueous sols such as boehmite, TiO 2 -, ZrO 2 - or SiO 2 sols, but also other aqueous sols of compounds of the main and subgroup metals are reacted with organically modified alkoxysilanes such that after stripping the solvent and optionally the subsequent dispersion of the liquid residue in water, clear solutions are obtained which are stable over a longer period.
- This removal of the solvent (alcohol) is required to guide the reaction of the coating of the particles with the organically modified alkoxysilanes so that a hydrolysis and condensation stable liquid system is formed.
- An object of the present invention is accordingly a process for the preparation of a composition for the provision of nanostructured molded articles and layers, which is as defined in claim 1 and characterized in that the alcohol is removed in such an amount that the residual alcohol content of the Composition is not more than 20 wt .-%, preferably not more than 15 wt .-% and in particular not more than 10 wt .-% makes.
- the present invention also relates to the compositions obtainable by the above process (only for the Contracting States AT, DE, DK, FI, GR, IE) and the use thereof for the production of nanostructured moldings and substrates provided with nanostructured layers.
- the process of the present invention differs from similar prior art processes in that a significant portion of the solvent (alcohol) present in the system is removed from the system. As a result, the hydrolysis and condensation equilibrium is shifted to the product side and a stabilization of the corresponding liquid system is achieved.
- at least 30% by weight, in particular at least 50% by weight and preferably at least 70% by weight, of the theory of the alcohol formed by hydrolysis of alkoxy groups is removed. More preferably at least 80% by weight and more preferably 90% by weight of this alcohol is removed.
- the originally present alcohol eg from the sol starting material
- the corresponding amount of alcohol is 100% removed
- the removal of the alcohol from the reaction system is preferably carried out under reduced pressure, so that an excessive thermal load of the system can be avoided.
- a temperature of 60 ° C, especially 50 ° C and more preferably 40 ° C, should not be exceeded.
- the sol used may be either an aqueous or an alcoholic or an aqueous / alcoholic sol. Preference is given to using purely aqueous sols.
- the alcohol is preferably one having from 1 to 4 carbon atoms, i. Methanol, ethanol, propanol, isopropanol and the butanols.
- the sol of the invention contains one or more compounds (preferably a compound) of one or more elements selected from silicon and the main and subgroup metals.
- the main and subgroup metals are preferably those from the third and fourth main group (in particular Al, Ga, Ge and Sn) and the third to fifth subgroup of the Periodic Table (in particular Ti, Zr, Hf, V, Nb and Ta).
- other metal compounds can also lead to advantageous results, such as those of Zn, Mo and W.
- the corresponding elemental compounds are oxides of oxide hydrates. Accordingly, it is at present in the compounds used in the invention Sol particular (and preferred) to SiO 2, Al 2 O 3, AlOOH (especially boehmite), TiO 2, ZrO 2 and mixtures thereof.
- the sol used in the process of the invention generally has a solids content of 5 to 50 wt .-%, preferably 10 to 40 and particularly preferably 15 to 30 wt .-%, on.
- the species with hydrolyzable alkoxy groups to be used in the process according to the invention include at least one organically modified alkoxysilane or a precondensate derived therefrom.
- Organically modified alkoxysilanes are those of the general formula (I): R ' 4-x Si (OR) x (I) in which the radicals R, identical or different from each other (preferably the same), represent optionally substituted (preferably unsubstituted) hydrocarbon groups having 1 to 8, preferably 1 to 6 and particularly preferably 1 to 4 carbon atoms (in particular methyl or ethyl), the radicals R ' , the same or different from each other, each represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms and x is 1, 2 or 3.
- This grouping capable of polyaddition or polycondensation reaction is an epoxy group.
- organo-modified alkoxysilanes of general formula (I) for use in the present invention are those in which x is 2 or 3 and more preferably 3 and a radical (the only radical) R 'is for ⁇ -glycidyloxy-C 2-6 -alkyl.
- silanes are 3-glycidoxypropyltri (m) ethoxysilane, 3,4-epoxybutyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
- alkoxysilanes which can preferably be used in combination with alkoxysilanes having the above groups capable of polyaddition or polycondensation reaction are, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, cyclohexyltrimethoxysilane, cyclopentyltrimethoxysilane, ethyltrimethoxysilane, phenylethyltrimethoxysilane, Phenyltrimethoxysilane, n-propyttrimethoxysilane, cyclohexylmethyldimethoxysilane, dimethyldimethoxysilane, diisopropyldimethoxysilane, phenylmethyldimethoxysilane, phenylethyltriethoxysilane, phenyltriethoxysi
- silanes can be used together with the organically modified alkoxysilane, via directly bonded to silicon fluorinated alkyl radicals having at least 4 carbon atoms (and preferably at least 3 fluorine atoms), wherein the carbon atoms in ⁇ and ⁇ position to the silicon preferably do not carry fluorine atoms, eg (Tridecafluoro-1,1,2,2-tetrahydrooctyl) methyldiethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) methyldiethoxysilane and (heptadecafluoro-1, 1,2,2-tetrahydrodecyl) triethoxysilane.
- silicon fluorinated alkyl radicals having at least 4 carbon atoms (and preferably at least 3 fluorine atoms)
- the species having hydrolyzable alkoxy groups employed in the present invention may include, in addition to the above silanes (especially the organically modified ones), also different species of silanes.
- examples of these are alkoxides (preferably with C 1-4 -alkoxy groups) of aluminum, titanium, zirconium, tantalum, niobium, tin, zinc, tungsten, germanium and boron.
- Such compounds are aluminum sec-butoxide, titanium isopropoxide, Titanium propoxide, titanium butoxide, zirconium isopropoxide, zirconium propoxide, zirconium butoxide, zirconium ethoxide, tantalum ethoxide, tantalum butoxide, niobium ethoxide, niobium butoxide, tin t-butoxide, tungsten (VI) ethoxide, germanium ethoxide, germanium isopropoxide and di-t-butoxyaluminotriethoxysilane.
- the more reactive alkoxides e.g., Al, Ti, Zr, etc.
- suitable complexing agents e.g. unsaturated carboxylic acids and ⁇ -dicarbonyl compounds, e.g. Methacrylic acid, acetylacetone and ethyl acetoacetate.
- the molar ratio of the organically modified alkoxysilanes to the different species is preferably at least 2: 1, in particular at least 5: 1 and particularly preferably at least 10: 1.
- the molar ratio of starter to organic group usually not exceeding 0.15: 1 ,
- starters are in particular imidazoles, amines, acid anhydrides and Lewis acids.
- imidazoles 1-methylimidazole is particularly preferred.
- imidazole starters are 2-methylimidazole and 2-phenylimidazole.
- initiators from the group of primary, secondary and tertiary amines are ethylenediamine, diethylenetriamine, triethylenetetramine, 1,6-diaminohexane, 1,6-bis (dimethylamino) hexane, tetramethylethylenediamine, N, N, N ', N ", N" Pentamethyldiethylenetriamine, 1,4-diazabicyclo [2.2.2] octane, cyclohexane-1,2-diamine, 2- (aminomethyl) -3,3,5-trimethylcyclopentylamine, 4,4'-diaminocyclohexylmethane, 1,3-bis (aminomethyl) cyclohexane, bis (4-amino-3-methylcyclohexyl) methane, 1,8-diamino-p-menthane, 3- (aminoethyl) -3,3,5-trimethylcyclohexyl
- the amines used as initiators can also be functionalized with silanes. Examples of these are N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, aminopropyltrimethoxysilane and aminopropyltriethoxysilane.
- silanes examples of these are N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, aminopropyltrimethoxysilane and aminopropyltriethoxysilane.
- boron trifluoride adducts of amines such as BF 3 -ethylamine, may be employed.
- organic crosslinking by means of acid anhydrides (preferably in combination with tertiary amines), such as ethylbicyclo [2.2.1] heptene-2,3-dicarboxylic anhydride, hexahydronaphthalene dicarboxylic anhydride, phthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, but also [3- (triethoxysilyl ) -propyl] succinic anhydride.
- acid anhydrides preferably in combination with tertiary amines
- suitable catalysts for the crosslinking of epoxy groups in the present case are (optionally prehydrolyzed) alkoxides of aluminum, titanium and zirconium, for example Al (OC 2 H 4 OC 4 H 9 ) 3 , and organic carboxylic acids, such as propionic acid.
- nanostructured molded articles and layers having hydrophilic properties are desired, it is possible, for example, to additionally incorporate components into the composition according to the invention which lead to such hydrophilic properties.
- components covalently attached to the inorganic matrix for example, a component having a free hydroxy group such as (meth) acrylic acid 2-hydroxyethyl ester
- a hydrophilic component e.g., a surfactant
- catalysts for the hydrolysis (and condensation) of the alkoxy groups are present.
- Preferred catalysts for this purpose are acid catalysts, e.g. aqueous (mineral) acids, e.g. HCl.
- the quantitative ratio of the starting materials used is preferably chosen so that in the final molded body or in the final layer (after curing) of the Sol resulting solids content of 1 to 50 wt .-% and in particular 5 to 30 wt .-% of the molding or the layer makes up.
- the method of contacting the aqueous and / or alcoholic sol with the species having hydrolyzable alkoxy groups under conditions which result in hydrolysis of the species with alkoxy groups will be apparent to those skilled in the art and further illustrated in the following examples.
- the solvent alcohol
- the viscosity of the composition in particular for coating purposes, is preferably below 5000 mPas, in particular below 3000 mPas.
- nanostructured moldings and substrates provided with nanostructured layers with the aid of the composition according to the invention are either incorporated in a mold or onto a substrate and subsequently - optionally after preceding drying at room temperature or slightly elevated temperature, in particular in the case of production of layers - a thermal (and optionally in addition a photochemical) curing by.
- all conventional coating methods can be used, e.g. Dipping, flooding, rolling, spraying, doctoring, spinning or screen printing.
- the curing temperature is usually in the range of 90 ° C to 300 ° C, in particular 110 ° C to 200 ° C, in the case of the layer production in particular also dependent on the temperature resistance of the substrate to be coated.
- the composition according to the invention is suitable for coating a wide variety of substrates and, in many cases, even without surface treatment, exhibits very good adhesion and extraordinarily high scratch resistance.
- Particularly preferred substrates for the layer production are glass, non-transparent and transparent plastics and metals.
- suitable plastics are polycarbonate, poly (meth) acrylates, polystyrene, polyvinyl chloride, polyethylene terephthalate, polypropylene and polyethylene, while a preferred metal substrate is aluminum.
- compositions are suitable for a variety of applications.
- examples are in particular the following:
- the resulting system coated polycarbonate and aluminum plates as well as CR-39 lenses were pretreated by corona discharge.
- the coated polycarbonate and aluminum plates were cured for 30 minutes at room temperature for 4 hours at 130 ° C.
- the CR-39 lenses were cured for 30 minutes at room temperature for 4 hours at 90 ° C.
- Example 1 was repeated, but 3.05 g (0.001 mol) of [3- (triethoxysilyl) propyl] succinic anhydride (GF20) were used instead of DIAMO. Examination of the abrasion resistance of polycarbonate sheets coated with this composition revealed Bem Taber abrasion test (roll stock CS 10F, 1000 cycles, roll load 500 g) 7% scattered light loss.
- GF20 [3- (triethoxysilyl) propyl] succinic anhydride
- Example 1 was repeated except that a boehmite suspension (2.78 g of Disperal® P3 in 25 g of distilled water) was used instead of the silica sol.
- Example 3 was repeated except that 3.78 g (0.01 mol) of Al (OEtOBu) 3 were used as catalyst instead of DIAMO.
- TiO 2 -containing sol 28.42 g (0.1 mol) of tetraisopropyl orthotitanate (Ti (OiPr) 4 ) were dissolved in 60 ml of isopropanol and admixed with concentrated hydrochloric acid in a molar ratio of 1: 1. After stirring at room temperature for 2 hours, the volatiles were removed by rotary evaporation and the residue was taken up in 70 ml of water.
- Ti (OiPr) 4 tetraisopropyl orthotitanate
- Corona discharge pretreated polycarbonate sheets and plasma pretreated CR-39 lenses were coated with the composition so prepared and cured thermally at 130 ° C and 90 ° C for one hour.
- Example 1 was repeated, but instead of DIAMO 1.32 g (0.005 mol) of trimethoxysilylpropyldiethylenetriamine (TRIAMO) were used.
- Example 1 was repeated but using 0.74 g (0.01 mol) of propionic acid as starter instead of DIAMO.
- Example 1 was repeated except that 3.87 g (0.01 mol) of Al (OEtOBu) 3 were used as starter instead of DIAMO.
- Example 1 was repeated but using 0.41 g (0.005 mol) of 1-methylimidazole as starter instead of DIAMO.
- Example 1 was repeated except that instead of DIAMO, 5.27 g (0.01 mol) of a mixture obtained by combining 3-aminopropyltriethoxysilane (AMEO) with GF20 in a molar ratio of 1: 1 under ice-cooling was used.
- DIAMO 3-aminopropyltriethoxysilane
- Example 6 was repeated except that 95.5 g of the silica sol described in Example 1 were used instead of the HCl-acid boehmite suspension and the amount of catalyst was quintupled.
- Corona discharge pretreated polycarbonate sheets and plasma pretreated CR-39 lenses were coated with the resulting composition and thermally cured at 130 ° C and 90 ° C for one hour.
- the resulting composition was coated with polycarbonate and aluminum plates and CR-39 lenses.
- the polycarbonate sheets were pretreated by corona discharge.
- the coated polycarbonate and aluminum plates were cured for 30 minutes at room temperature for 4 hours at 130 ° C.
- the CR-39 lenses were cured after 30 minutes at room temperature for 4 hours at 90 ° C.
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Claims (16)
- Procédé de préparation d'une composition destinée à la fabrication de corps moulés ou de couches à nanostructures, comportant le fait de mettre un sol aqueux et/ou alcoolique d'un composé d'un élément choisi parmi le silicium et les métaux des groupes principaux et des groupes secondaires, le composé constituant le sol étant un oxyde ou hydrate d'oxyde au nombre d'au moins un, en contact avec une espèce comportant des groupes alcoxy hydrolysables, qui comprend au moins un alcoxy-silane à modification organique ou un précondensat qui en dérive, dans des conditions qui conduisent à une (post)hydrolyse de cette espèce, et le fait d'éliminer ensuite l'alcool formé ainsi que l'alcool qui était éventuellement déjà présent au départ, lequel procédé est caractérisé en ce que la quantité d'alcool éliminée est telle que l'alcool restant dans la composition ne représente pas plus de 20 % du poids de celle-ci, et en ce que l'alcoxysilane à modification organique comprend au moins un composé de formule générale (I) :
R'4-xSi(OR)x (I)
dans laquelle les restes représentés par R sont des groupes hydrocarbonés comportant 1 à 8 atomes de carbone, éventuellement substitués, les restes représentés par R', qui sont identiques ou différents, sont des groupes hydrocarbonés comportant 1 à 20 atomes de carbone, éventuellement substitués, et x vaut 1, 2 ou 3, étant entendu qu'au moins l'un des restes représentés par R' comporte un groupe pouvant donner lieu à une réaction de polyaddition ou de polycondensation, qui est un groupe époxyde. - Procédé conforme à la revendication 1, dans lequel la quantité d'alcool éliminée est une quantité qui correspond à la quantité totale d'alcool éventuellement déjà présent au départ, augmentée d'au moins 30 %, et en particulier d'au moins 50 %, du poids d'alcool qui peut être théoriquement formé par hydrolyse de tous les groupes alcoxy présents au départ.
- Procédé conforme à l'une des revendications 1 et 2, dans lequel, après avoir éliminé l'alcool, on ajoute de l'eau à la composition pour en ajuster la viscosité à une valeur appropriée.
- Procédé conforme à l'une des revendications 1 à 3, dans lequel on utilise un sol aqueux.
- Procédé conforme à l'une des revendications 1 à 4, dans lequel les composés constituant le sol dérivent d'au moins un élément choisi parmi le silicium et les métaux des groupes principaux III et IV et des groupes secondaires III à V du Tableau Périodique, et en particulier de Si, Al, Sn, Ti ou Zr.
- Procédé conforme à l'une des revendications 1 à 5, dans lequel le sol est un sol de SiO2, Al2O3, AlOOH, TiO2 et/ou ZrO2.
- Procédé conforme à l'une des revendications 1 à 6, dans lequel, dans l'alcoxysilane à modification organique de formule générale (I), les symboles R représentent des groupes alkyle en C1-4, en particulier des groupes méthyle ou éthyle, et x vaut 2 ou 3, en particulier 3.
- Procédé conforme à l'une des revendications 1 à 7, dans lequel le reste représenté par R', ou au moins l'un des restes représentés par R', est un groupe ω-glycidyloxy-(alkyle en C2-6).
- Procédé conforme à l'une des revendications 1 à 8, dans lequel on ajoute à la composition un catalyseur pour la réaction de polyaddition ou de polycondensation.
- Procédé conforme à l'une des revendications 1 à 9, dans lequel les conditions qui conduisent à une (post)hydrolyse de l'espèce comportant des groupes alcoxy hydrolysables comprennent la présencea) d'au moins 0,5 mole de H2O par mole de groupes alcoxy hydrolysables,b) et d'un catalyseur, de préférence acide, pour la réaction d'hydrolyse.
- Procédé conforme à l'une des revendications 1 à 10, dans lequel on utilise le sol en une quantité telle que, dans le corps moulé final ou dans la couche finale, la quantité de matières solides provenant du sol représente de 1 à 50 %, et en particulier de 5 à 30 %, du poids du corps moulé ou de la couche.
- Procédé de fabrication de corps moulés à nanostructures ou de substrats porteurs de couches à nanostructures, dans lequela) on met dans un mouleb) ou l'on dépose sur un substrat
une composition préparée selon un procédé conforme à l'une des revendications 1 à 11, puis on la fait durcir par voie thermique, et en plus, le cas échéant, par voie photochimique. - Procédé conforme à la revendication 12, dans lequel le substrat est un substrat en verre, en matière plastique ou en métal.
- Corps moulés à nanostructures ou substrats porteurs de couches à nanostructures, accessibles par un procédé conforme à l'une des revendications 12 et 13.
- Utilisation de corps moulés à nanostructures ou de substrats porteurs de couches à nanostructures, conformes à la revendication 14, dans des applications optiques.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE19816136A DE19816136A1 (de) | 1998-04-09 | 1998-04-09 | Nanostrukturierte Formkörper und Schichten und deren Herstellung über stabile wasserlösliche Vorstufen |
DE19816136 | 1998-04-09 | ||
PCT/EP1999/002396 WO1999052964A2 (fr) | 1998-04-09 | 1999-04-08 | Corps moules et couches nanostructures et leur production a l'aide de precurseurs stables solubles dans l'eau |
Publications (3)
Publication Number | Publication Date |
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EP1086162A2 EP1086162A2 (fr) | 2001-03-28 |
EP1086162B1 EP1086162B1 (fr) | 2004-11-10 |
EP1086162B2 true EP1086162B2 (fr) | 2013-11-20 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP99920614.7A Expired - Lifetime EP1086162B2 (fr) | 1998-04-09 | 1999-04-08 | Corps moules et couches nanostructures et leur production a l'aide de precurseurs stables solubles dans l'eau |
Country Status (17)
Country | Link |
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US (1) | US6620514B1 (fr) |
EP (1) | EP1086162B2 (fr) |
JP (1) | JP4597368B2 (fr) |
KR (1) | KR20010042528A (fr) |
CN (1) | CN1145659C (fr) |
AT (1) | ATE282058T1 (fr) |
AU (1) | AU3813899A (fr) |
BR (1) | BR9909521A (fr) |
CA (1) | CA2327312A1 (fr) |
CZ (1) | CZ20003683A3 (fr) |
DE (2) | DE19816136A1 (fr) |
ES (1) | ES2232135T5 (fr) |
HU (1) | HUP0101496A3 (fr) |
MX (1) | MXPA00009735A (fr) |
NO (1) | NO331461B1 (fr) |
PL (1) | PL213503B1 (fr) |
WO (1) | WO1999052964A2 (fr) |
Families Citing this family (84)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19846659C2 (de) * | 1998-10-09 | 2001-07-26 | Wkp Wuerttembergische Kunststo | Schichtwerkstoff und Verfahren zum Herstellen eines solchen |
DE19909894A1 (de) | 1999-03-06 | 2000-09-07 | Basf Coatings Ag | Sol-Gel-Überzug für einschichtige oder mehrschichtige Lackierungen |
DE19940858A1 (de) | 1999-08-27 | 2001-03-01 | Basf Coatings Ag | Sol-Gel-Überzug für einschichtige oder mehrschichtige Lackierungen |
DE29918102U1 (de) | 1999-10-14 | 2000-01-13 | Rational Einbauküchen GmbH, 49328 Melle | Beschichtete Platte für ein Küchen- oder Badmöbel |
DE19958336A1 (de) * | 1999-12-03 | 2001-06-07 | Inst Neue Mat Gemein Gmbh | Selbstvernetzende Beschichtungszusammensetzungen auf Basis anorganischer fluorhaltiger Polykondensate |
DE10018671C2 (de) * | 2000-04-14 | 2002-09-26 | Nanogate Technologies Gmbh | Verfahren zur Erzeugung einer hydrophoben Oberfläche von Gegenständen aus silikatkeramischen Werkstoffen sowie Gegenstand mit einer hydrophoben Oberfläche |
DE10063519A1 (de) * | 2000-12-20 | 2002-07-04 | Nano X Gmbh | Lösungsmittelarme Sol-Gel-Systeme |
EP1236765A1 (fr) | 2001-02-28 | 2002-09-04 | hanse chemie GmbH | Dispersion de silice |
DE10134473B4 (de) | 2001-07-16 | 2007-11-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur Beschichtung passivierter metallischer Oberflächen aus Chrom von Bauteilen sowie derart beschichtetes Bauteil und Verwendung des Verfahrens |
DE10154030A1 (de) * | 2001-11-02 | 2003-05-22 | Basf Coatings Ag | Effektgeber, wässriger Beschichtungsstoff, Verfahren zu seiner Herstellung und seine Verwendung |
DE10200929A1 (de) * | 2002-01-12 | 2003-07-31 | Basf Coatings Ag | Polysiloxan-Sole, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE10221007B4 (de) * | 2002-05-11 | 2016-10-13 | Basf Coatings Gmbh | Wässrige Dispersion von anorganischen Nanopartikeln, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE10221009B4 (de) * | 2002-05-11 | 2016-10-13 | Basf Coatings Gmbh | Beschichtungsstoffe, deren Verwendung, Verfahren zur Herstellung von Beschichtungen und transparente Beschichtungen |
DE10221010A1 (de) * | 2002-05-11 | 2003-11-27 | Basf Coatings Ag | Wässrige Dispersion von anorganischen Nanopartikeln, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE10234588A1 (de) * | 2002-07-30 | 2004-02-19 | Robert Bosch Gmbh | Bauteil eines Verbrennungsmotors mit einem tribologisch beanspruchten Bauelement |
DE10253841A1 (de) * | 2002-11-14 | 2004-05-27 | Hansgrohe Ag | Beschichtungsverfahren |
DE10253839A1 (de) * | 2002-11-14 | 2004-05-27 | Hansgrohe Ag | Beschichtungsverfahren |
DE10308949B4 (de) * | 2003-02-28 | 2008-12-11 | BAM Bundesanstalt für Materialforschung und -prüfung | Verfahren zur Herstellung von anorganisch modifizierten cellulosehaltigen Werkstoffen sowie anorganisch modifizierter Werkstoff |
DE10313630A1 (de) * | 2003-03-26 | 2004-10-07 | BSH Bosch und Siemens Hausgeräte GmbH | Glasartige Bedruckung mittels Siebdruck |
US20060191671A1 (en) * | 2003-03-31 | 2006-08-31 | Behr Gmbh & Co. Kg | Heat exchanger and method for treating the surface of said heat exchanger |
DE10320431A1 (de) | 2003-05-08 | 2004-12-16 | Basf Coatings Ag | Epoxyfunktionelle Silane, Verfahren zur ihrer Herstellung und ihre Verwendung |
ATE388282T1 (de) * | 2003-09-03 | 2008-03-15 | Perlen Converting Ag | Flammhemmfolie |
DE10348954B3 (de) * | 2003-10-18 | 2005-01-05 | Clariant Gmbh | Verfahren zur Herstellung von Beschichtungsformulierungen für wasser- und ölabweisende Beschichtungen |
DE10351251B3 (de) * | 2003-11-03 | 2005-05-19 | Basf Coatings Ag | Strukturviskose, wässrige Dispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE10353507A1 (de) * | 2003-11-17 | 2005-06-30 | Basf Coatings Ag | Hydrolysate und/oder Kondensate von Epoxid- und Silangruppen enthaltenden Oligomeren und Polymeren, Verfahren zu ihrer Herstellung und ihre Verwendung |
US20050104338A1 (en) * | 2003-11-19 | 2005-05-19 | Quin Soderquist | Applique film airbag cover |
DE10357116A1 (de) | 2003-12-06 | 2005-07-07 | Solvay Barium Strontium Gmbh | Desagglomeriertes Bariumsulfat |
DE102004008772A1 (de) * | 2004-02-23 | 2005-09-08 | Institut für Neue Materialien Gemeinnützige GmbH | Abriebbeständige und alkalibeständige Beschichtungen oder Formkörper mit Niedrigenergieoberfläche |
DE102004009287A1 (de) * | 2004-02-26 | 2005-09-15 | Institut Für Neue Materialien Gem. Gmbh | Amphiphile Nanopartikel |
MXPA06010676A (es) * | 2004-03-19 | 2007-02-21 | Doerken Ewald Ag | Microrevestimiento comprendiendo siloxanos. |
US20070212534A1 (en) * | 2004-03-31 | 2007-09-13 | Nippon Sheet Glass Company, Limited | Article With Silica-Based Film and Process for Producing the Same |
DE102004022400A1 (de) * | 2004-05-06 | 2005-12-15 | Consortium für elektrochemische Industrie GmbH | Feuchtigkeitsvernetzbare alkoxysilyfunktionelle Partikel enthaltende Zusammensetzung |
DE102004036073A1 (de) * | 2004-07-24 | 2006-02-16 | Degussa Ag | Verfahren zur Versiegelung von Natursteinen |
DE102004037045A1 (de) * | 2004-07-29 | 2006-04-27 | Degussa Ag | Wässrige Silan-Nanokomposite |
CN101072812A (zh) | 2004-10-12 | 2007-11-14 | Sdc涂料有限公司 | 涂料组合物、制品以及涂覆制品的方法 |
AU2006223513B2 (en) * | 2005-03-09 | 2009-08-13 | Astenjohnson, Inc. | Papermaking fabrics with contaminant resistant nanoparticle coating and method of in situ application |
DE102005012457B3 (de) | 2005-03-18 | 2006-08-31 | Basf Coatings Ag | Epoxid- und Silangruppen enthaltende Oligomere und Polymere, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE102006006655A1 (de) * | 2005-08-26 | 2007-03-01 | Degussa Ag | Cellulose- bzw. lignocellulosehaltige Verbundwerkstoffe auf der Basis eines auf Silan basierenden Komposits als Bindemittel |
CN101277815A (zh) * | 2005-10-05 | 2008-10-01 | 日本板硝子株式会社 | 形成有有机无机复合膜的物品 |
DE102005052939A1 (de) * | 2005-11-03 | 2007-05-10 | Degussa Gmbh | Herstellung von beschichteten Substraten |
DE102005056620A1 (de) * | 2005-11-25 | 2007-06-06 | Merck Patent Gmbh | Amphiphile Silane |
EP1979428B1 (fr) * | 2005-12-23 | 2011-02-23 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Composition de revêtement mécaniquement stable et facile à nettoyer pour des surfaces métalliques et procédé servant à former un revêtement sur un substrat en utilisant ladite composition |
DE102006003957A1 (de) * | 2006-01-26 | 2007-08-02 | Degussa Gmbh | Wasserverdünnbare Sol-Gel-Zusammensetzung |
DE102006003956A1 (de) * | 2006-01-26 | 2007-08-02 | Degussa Gmbh | Korrossionsschutzschicht auf Metalloberflächen |
KR100745745B1 (ko) * | 2006-02-21 | 2007-08-02 | 삼성전기주식회사 | 나노복합재료 및 그 제조방법 |
BRPI0710795A2 (pt) | 2006-04-27 | 2011-06-21 | Sachtleben Chemie Gmbh | camada de fundo endurecìvel por uv, processo para sua produção, uso da mesma e processo para revestimento de superfìcies |
DE102006024727A1 (de) | 2006-05-26 | 2007-11-29 | Cht R. Beitlich Gmbh | Mit Wasser verdünnbares Konzentrat zur Beschichtung verschiedener Substrate |
DE102006027480A1 (de) * | 2006-06-14 | 2008-01-10 | Evonik Degussa Gmbh | Kratz- und abriebfeste Beschichtungen auf polymeren Oberflächen |
DE102007020404A1 (de) * | 2006-09-18 | 2008-10-30 | Nano-X Gmbh | Verfahren zur Herstellung eines Beschichtungsmaterials |
DE102008014717A1 (de) | 2006-09-18 | 2009-09-24 | Nano-X Gmbh | Verfahren zur Herstellung eines hoch abriebfesten Fahrzeuglackes, Fahrzeuglack und dessen Verwendung |
DE102006044310A1 (de) * | 2006-09-18 | 2008-03-27 | Nano-X Gmbh | Silanbeschichtungsmaterial und Verfahren zur Herstellung eines Silanbeschichtungsmaterials |
WO2008075650A1 (fr) * | 2006-12-20 | 2008-06-26 | Nippon Sheet Glass Company, Limited | Objet doté d'un film de composites organique et inorganique |
FR2914631B1 (fr) | 2007-04-06 | 2009-07-03 | Eads Europ Aeronautic Defence | Materiau nanostructure particulier, comme revetement protecteur de surfaces metalliques. |
US8569420B2 (en) * | 2007-06-19 | 2013-10-29 | The University Of Akron | Singly-terminated polyisobutylenes and process for making same |
US20090104438A1 (en) * | 2007-10-17 | 2009-04-23 | Jennifer Hoyt Lalli | Abrasion resistant coatings |
DE102007054627A1 (de) | 2007-11-15 | 2009-05-20 | Cht R. Beitlich Gmbh | Wasserverträgliche Sole zur Beschichtung verschiedener Substrate |
DE102007058712A1 (de) | 2007-12-06 | 2009-06-10 | Evonik Degussa Gmbh | Modulares Sol-Gel-System und Verfahren zum Einstellen der Eigenschaften des Sol-Gel-Systems |
CN101235284B (zh) * | 2008-02-04 | 2011-11-09 | 厦门大学 | 溶胶-凝胶固定水溶性量子点的方法 |
EP2096151A1 (fr) | 2008-02-27 | 2009-09-02 | Degussa Novara Technology S.p.A. | Composition |
JP5520237B2 (ja) * | 2008-03-03 | 2014-06-11 | ユニバーシティ オブ フロリダ リサーチ ファンデーション インコーポレーティッド | ナノ粒子ゾル−ゲル複合ハイブリッドの透明コーティング材料 |
DE102008031360A1 (de) | 2008-07-04 | 2010-01-14 | K+S Ag | Verfahren zum Herstellen von aushärtbaren Massen, enthaltend grob- und/oder nanoskalige, gecoatete, desagglomerierte und bevorzugt funktionalisierte Magnesiumhydroxidpartikel, sowie von ausgehärteten thermoplastischen oder duroplastischen Polymeren bzw. Kompositen, enthaltend desagglomerierte und homogen verteilte Magnesiumhydroxidfüllstoffpartikel |
EP2342298A4 (fr) * | 2008-10-31 | 2013-01-16 | Univ Florida | Matériaux hybrides inorganiques-organiques transparents obtenus par un traitement sol-gel aqueux |
JP5072820B2 (ja) * | 2008-12-22 | 2012-11-14 | 日東電工株式会社 | シリコーン樹脂組成物 |
CN102341463B (zh) * | 2009-03-13 | 2014-06-11 | 阿克佐诺贝尔化学国际公司 | 硅烷化二氧化硅水分散体 |
CN101941001B (zh) | 2009-07-03 | 2014-04-02 | 3M创新有限公司 | 亲水涂层、制品、涂料组合物和方法 |
DE102010030115A1 (de) | 2009-08-11 | 2011-02-17 | Evonik Degussa Gmbh | Glycidyloxyalkylalkoxysilan-basierte wässrige Silansysteme für den Blankkorrosionsschutz und Korrosionsschutz von Metallen |
JP5182535B2 (ja) * | 2010-05-28 | 2013-04-17 | 信越化学工業株式会社 | 水性シロキサン塗料組成物及びその製造方法、表面処理剤、表面処理鋼材並びに塗装鋼材 |
EP2591060B1 (fr) * | 2010-07-09 | 2016-12-21 | Luna Innovations Incorporated | Systèmes de revêtement capables de former, sur des substrats, des revêtements hydrophobes hautement durables durcis à la température ambiante |
CN103002993B (zh) | 2010-07-28 | 2015-06-03 | 巴斯夫欧洲公司 | 珍珠岩基效应颜料在具有古旧或绿锈外观的涂层中的用途 |
DE102011101179A1 (de) | 2011-05-11 | 2012-11-15 | Fachhochschule Kiel | Beschichtungen für Polymere |
US20130034722A1 (en) * | 2011-08-01 | 2013-02-07 | Intermolecular, Inc. | Sol-gel based antireflective coatings using particle-binder approach with high durability, moisture resistance, closed pore structure and controllable pore size |
DE102012111836A1 (de) * | 2012-12-05 | 2014-06-05 | Schott Ag | Beschichtungsmaterial und Substrat mit einer semitransparenten Beschichtung |
US20190233674A1 (en) * | 2016-09-09 | 2019-08-01 | Mirapakon Inc. | Hydrophobic Xerogel Film and Method of Use Thereof For Reducing Condensation |
CN109433174B (zh) * | 2018-10-16 | 2021-11-12 | 上海申得欧有限公司 | 硅酸盐包覆二氧化钛光触媒粉体及其制备方法 |
DE102019203079A1 (de) * | 2019-03-06 | 2020-09-10 | Henkel Ag & Co. Kgaa | Verfahren zur Herstellung und Anwendung von Haarbehandlungsmitteln mit organischen C1-C6-Alkoxy-Silanen |
JP7467866B2 (ja) * | 2019-10-02 | 2024-04-16 | 住友ゴム工業株式会社 | 親水性基材及び親水性基材作製方法 |
CN110698679A (zh) * | 2019-11-04 | 2020-01-17 | 哈尔滨工业大学 | 一种主链掺锆的绿色环保耐高温杂化有机硅树脂及其制备方法 |
DE102020125920B4 (de) | 2020-10-04 | 2022-05-19 | Elke Münch | Durch eine Temperaturdifferenz betreibbare, mobile Vorrichtung zur Reinigung und Desinfizierung von Raumluft |
EP3981442A1 (fr) | 2020-10-04 | 2022-04-13 | Elke Münch | Dispositif mobile de nettoyage et de désinfection de l'air ambiant pouvant fonctionner par différence de température |
DE102020125921B4 (de) | 2020-10-04 | 2022-05-19 | Elke Münch | Durch eine Temperaturdifferenz betreibbare, mobile Vorrichtung zur Reinigung und Desinfizierung von Raumluft |
EP3978038A1 (fr) | 2020-10-04 | 2022-04-06 | Elke Münch | Dispositif mobile de nettoyage et de désinfection de l'air ambiant pouvant fonctionner par différence de température et dispositif d'essai associé |
DE102020125922B4 (de) | 2020-10-04 | 2022-06-02 | Elke Münch | Mobile Vorrichtung zur Reinigung und Desinfizierung von Raumluft |
DE102020125919B4 (de) | 2020-10-04 | 2022-06-23 | Elke Münch | Durch eine Temperaturdifferenz betreibbare, mobile Vorrichtung zur Reinigung und Desinfizierung von Raumluft und eine Testvorrichtung hierfür |
DE102022001868A1 (de) | 2022-05-29 | 2023-11-30 | Elke Hildegard Münch | Biozid beschichtete, retikulierte Schaumstoffe aus Kunststoff, Verfahren zu ihrer Herstellung und ihre Verwendung |
Family Cites Families (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1963439A1 (de) * | 1969-12-18 | 1971-06-24 | Dynamit Nobel Ag | Verfahren zur Herstellung poroeser Kieselsaeure |
US3707397A (en) * | 1971-02-26 | 1972-12-26 | Owens Illinois Inc | Process for providing uniform organopolysiloxane coatings on polycarbonate and acrylic surfaces |
US3834924A (en) * | 1972-06-08 | 1974-09-10 | Huber Corp J M | Process for manufacturing surface modified inorganic pigments |
US4455205A (en) * | 1981-06-01 | 1984-06-19 | General Electric Company | UV Curable polysiloxane from colloidal silica, methacryloyl silane, diacrylate, resorcinol monobenzoate and photoinitiator |
JPS60177079A (ja) * | 1984-02-23 | 1985-09-11 | Toshiba Silicone Co Ltd | 被覆用組成物 |
JPS62256874A (ja) * | 1986-05-01 | 1987-11-09 | Toshiba Silicone Co Ltd | 紫外線硬化型組成物の製造方法 |
DE3751856T3 (de) * | 1986-10-03 | 2001-04-19 | Ppg Industries Ohio, Inc. | Organisch-anorganisches Hybridpolymer |
US4799963A (en) * | 1986-10-03 | 1989-01-24 | Ppg Industries, Inc. | Optically transparent UV-protective coatings |
IL84025A0 (en) * | 1986-10-03 | 1988-02-29 | Ppg Industries Inc | Organosiloxane/metal oxide coating compositions and their production |
US4814017A (en) * | 1986-10-03 | 1989-03-21 | Ppg Industries, Inc. | Aqueous organoalkoxysilane/metal oxide sol-gel compositions |
JPH02175732A (ja) * | 1988-12-28 | 1990-07-09 | Central Glass Co Ltd | 被覆用組成物、それを用いたプラスチック成形品およびその製造法 |
US5164003A (en) * | 1990-03-28 | 1992-11-17 | Ceram Tech International, Ltd. | Room temperature curable surface coating and methods of producing and applying same |
AU653825B2 (en) * | 1991-06-25 | 1994-10-13 | Itoh Optical Industrial Co., Ltd. | Coating composition for optical plastic moldings |
JP2520994B2 (ja) * | 1991-09-13 | 1996-07-31 | 松下電工株式会社 | 反射鏡の製造方法 |
JPH05170486A (ja) * | 1991-12-25 | 1993-07-09 | Central Glass Co Ltd | ガラス表面用撥水処理剤およびその撥水処理ガラス |
US5307438A (en) * | 1992-08-13 | 1994-04-26 | Minnesota Mining And Manufacturing Company | Index matching compositions with improved DNG/DT |
US5873931A (en) * | 1992-10-06 | 1999-02-23 | Minnesota Mining And Manufacturing Company | Coating composition having anti-reflective and anti-fogging properties |
JP3545439B2 (ja) * | 1993-10-13 | 2004-07-21 | 三菱レイヨン株式会社 | 紫外線硬化性被覆材の製法及びそれを用いた耐摩耗性被覆材組成物 |
JPH07207190A (ja) * | 1994-01-24 | 1995-08-08 | Shin Etsu Chem Co Ltd | 紫外線硬化性ハードコーティング剤及びプラスチック製光学物品 |
JPH08311401A (ja) * | 1995-03-01 | 1996-11-26 | Seiko Epson Corp | コーティング用組成物およびその製造方法および積層体 |
US5789476A (en) * | 1995-03-03 | 1998-08-04 | Seiko Epson Corporation | Film-forming coating solution and synthetic resin lens |
US5928127A (en) * | 1995-04-03 | 1999-07-27 | Asahi Glass Company Ltd. | Alumina sol and recording sheet |
JPH09194760A (ja) * | 1996-01-23 | 1997-07-29 | Mitsubishi Rayon Co Ltd | 被覆材組成物、それを用いてなる機能性に優れた物品、及びプラスチックレンズ |
JPH1025431A (ja) * | 1996-07-11 | 1998-01-27 | Kawaken Fine Chem Co Ltd | 無機塗料バインダー組成物および無機塗料組成物 |
JPH1025451A (ja) * | 1996-07-12 | 1998-01-27 | Shima Boeki Kk | 紫外線吸収性被覆用組成物 |
US5814137A (en) * | 1996-11-04 | 1998-09-29 | The Boeing Company | Sol for coating metals |
DE19708285C2 (de) * | 1997-02-28 | 2002-04-11 | Excor Korrosionsschutz Technol | Korrosionsinhibierendes Kompositmaterial, Verfahren zu dessen Herstellung und seine Verwendung |
US5789082A (en) * | 1997-03-12 | 1998-08-04 | The Walman Optical Company | Thermosetting coating composition |
DE19737328A1 (de) * | 1997-08-27 | 1999-03-04 | Bayer Ag | Beschichtungszusammensetzungen auf der Basis von Epoxidgruppen enthaltenden Silanen |
US6245833B1 (en) * | 1998-05-04 | 2001-06-12 | 3M Innovative Properties | Ceramer composition incorporating fluoro/silane component and having abrasion and stain resistant characteristics |
JP3982933B2 (ja) * | 1999-01-14 | 2007-09-26 | 触媒化成工業株式会社 | 被膜形成用塗布液および合成樹脂製レンズ |
-
1998
- 1998-04-09 DE DE19816136A patent/DE19816136A1/de not_active Ceased
-
1999
- 1999-04-08 AU AU38138/99A patent/AU3813899A/en not_active Abandoned
- 1999-04-08 US US09/647,971 patent/US6620514B1/en not_active Expired - Lifetime
- 1999-04-08 BR BR9909521-1A patent/BR9909521A/pt not_active Application Discontinuation
- 1999-04-08 KR KR1020007011168A patent/KR20010042528A/ko not_active Application Discontinuation
- 1999-04-08 EP EP99920614.7A patent/EP1086162B2/fr not_active Expired - Lifetime
- 1999-04-08 JP JP2000543519A patent/JP4597368B2/ja not_active Expired - Lifetime
- 1999-04-08 ES ES99920614.7T patent/ES2232135T5/es not_active Expired - Lifetime
- 1999-04-08 AT AT99920614T patent/ATE282058T1/de active
- 1999-04-08 CA CA002327312A patent/CA2327312A1/fr not_active Abandoned
- 1999-04-08 PL PL343590A patent/PL213503B1/pl unknown
- 1999-04-08 MX MXPA00009735A patent/MXPA00009735A/es unknown
- 1999-04-08 WO PCT/EP1999/002396 patent/WO1999052964A2/fr active IP Right Grant
- 1999-04-08 DE DE59911048T patent/DE59911048D1/de not_active Expired - Lifetime
- 1999-04-08 CZ CZ20003683A patent/CZ20003683A3/cs unknown
- 1999-04-08 CN CNB998063444A patent/CN1145659C/zh not_active Expired - Lifetime
- 1999-04-08 HU HU0101496A patent/HUP0101496A3/hu unknown
-
2000
- 2000-09-28 NO NO20004877A patent/NO331461B1/no not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
ATE282058T1 (de) | 2004-11-15 |
JP4597368B2 (ja) | 2010-12-15 |
NO331461B1 (no) | 2012-01-09 |
CN1145659C (zh) | 2004-04-14 |
ES2232135T3 (es) | 2005-05-16 |
DE59911048D1 (de) | 2004-12-16 |
HUP0101496A3 (en) | 2002-02-28 |
CZ20003683A3 (cs) | 2001-01-17 |
NO20004877D0 (no) | 2000-09-28 |
CA2327312A1 (fr) | 1999-10-21 |
EP1086162B1 (fr) | 2004-11-10 |
JP2002511509A (ja) | 2002-04-16 |
BR9909521A (pt) | 2000-12-12 |
KR20010042528A (ko) | 2001-05-25 |
AU3813899A (en) | 1999-11-01 |
US6620514B1 (en) | 2003-09-16 |
EP1086162A2 (fr) | 2001-03-28 |
CN1301277A (zh) | 2001-06-27 |
PL343590A1 (en) | 2001-08-27 |
DE19816136A1 (de) | 1999-10-14 |
PL213503B1 (pl) | 2013-03-29 |
NO20004877L (no) | 2000-09-28 |
ES2232135T5 (es) | 2014-02-24 |
WO1999052964A3 (fr) | 2000-01-20 |
MXPA00009735A (es) | 2002-04-24 |
HUP0101496A2 (hu) | 2001-08-28 |
WO1999052964A2 (fr) | 1999-10-21 |
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